Brown dyesttjffs suitable for dyeing wool and leather and process of



Patented May 7, 1 293.,

u'iTEn STATES mass ROBERT SCHMIDLIN, OF HOCHT-ON-THE-MAIN, GERMANY,ASSIGNOR, BY MESNE ASSIGNMENTS, TO GRASSELLI DYESTUFF CORPORATION,

A CORPORATION OF DELAWARE.

BROWN DYESTUFFS SUITABLE FOR DYEING WOOL AND LEATHER AND MAKING SAME.

or NEW YORKQN Y.,

PROCESS 0]! No Drawing. Application filed July 3, 1924 Serial No.724,130, and in Germany July 23, 1923.

' I have found that quinone derivatives of the type:

wherein R and R represent radicles of the products obtained by-thecondensation of chloronitroaryl sulfonic and carboxyllc acids whichgives an excellent deep brown shade; By enlarging the molecule, modifiedshades tion of benzoquinones with the said bodies may occur within widelimits as regards temperature and concentration. One representative ofthis class of dyestuffs is for instance the body of the formula:

SOaNa N0 NH- 01 NH (Example 1) I I NH- 01- N H N02 t I OaNa can beobtained. Thus, it is possible to obtain for instance by the dyestuff ofthe formula:

SOaNa -NH -N H C] -NH N O:

(Example 2) N O NH 01 NH NH OaNa g a brown tint with a green hue whichcould hitherto be obtained only by a mixture of different dyestuffs.

In View of the accumulation of anilido groups in the molecule it couldnot be pre sumed that bodies of sufficient solubility would be producedand having regard to the many ele'ct-ronegative constituents one couldnot expect that these dyestuffs would be fast to alkalis, a propertywhich they possess in a high degree.

The following examples illustrate my invention:

(1) 31 parts of 4-nitro-4-aminodiphenylamin-Q-sulfonic acid aredissolved in 400 parts of water by means of 10,6 parts of carbonate ofsodium and heated for some hours to about 90 C., while stirring, with 12parts of chloranil. After cooling, the solution is filtered off and thenwashed. The dyestuif forms a dark-brown powder which, when dissolved inconcentrated sulfuric acid and heated,

gives a blue solution which dyes Wool and leather brown shades. Theproduct has the probable formula:

,trodiphenylamino-sulfonate (obtained by condensation ofchlorodinitrobenzene-(1, 2,

4) with sodium 4, 4:-diaminodiphenylamin-2- sulfonate) are dissolved in400 parts of water and this solution is stirred for some hours at about90 C. with 12 parts of chloranil and 5,3 parts of sodium carbonate.After filtering and drying, the dyestud is obtained in yellow solutionwhich dyes leather with a the form of a black powder which, whendisdark-brown shade. r 5

solved in cone. sulfuric acid, gives a greenish- The product has theprobable formula:

I N01 o SO Na l c I N 01 N0: N0 r1114)... E @Q l toaNa t H NO: (3) 81parts of the body of the formula: and stirred for some hours at 90 C. in3000 NaOaS, a parts of Water and then salted out. The dyestud afterbeing pressed out and dried, dyes N leather tobacco-brown shades.

NO a 4 The product .has the probable formula:

and 42 parts of toluquinone are introduced I some o H N N CH3 H N0.

Nor- IiII-- N a I tt I toms (4) 21 parts of the body ofthe formula: 200parts of Water and stirred for one hour SOaNa at 90 C. The dyestuffafter being salted out and dried, dyes leather olive-brown shades.

NH NHZ The product has'the probable formula: 1 N09- 5 oina I v 25 and 9parts of toluquinone are dissolved in SOaN'a Y o' I 1 N N 0H3 on N0:

7 N03- A on N N a x I g (5) 32,3 parts of 5-methyl-4-amino-4'-niout anddried. It forms a dark-brown pow trodiphenylamine-2-sulfonic acid aredisder dissolving in conc. sulfuric acid to a solved with 5,3 parts ofsodium carbonate in brown solution which only changes slightly 350 partsof water, there are then added 18 when heated and which gives on leatherand parts of toluquinone and after heating on the wool a greenish browntint. 40

35 water-bath for.2 hours the dyestufi is salted The product has theprobable formula:

- A on; o .soaNa 1 I II If I 1 N0 H N CH3 N v N It i N02 I OaNa t) Ha IY I I 8,6 parts of (5-amino-1-naphthyl) -4,- dry state the dyestuifforms a black powder 6-dinitroaniline-2-sulfonate of sodium are whichdissolves -in conc. sulfuric acid to a I mixed and stirred with 4,2parts of toluquin-' brownsolution which gives on chrome leather m 4 onein 100 parts of Water at C. for 2 hours; a greenish-brown tint.

the mixture is then filtered and the filtrate The product has theprobable formula: precipitated by adding common salt. In a SQ Na '14) NoI cm I i i l N0 N0: A A i a a I GIN! 1,71 pace (7) 36 parts ofsodium-4-amino-5-methyl- 4c 6' dinitrodiphen'ylamine 2' carboxylate aredissolved, while hot, in 300 parts of water; there are then added 20parts of toluquinone and the mixture is stirred for one hour at 90 C. Aportion of the dyestuflf thus formed separates, the remainder is saltedout. The

COONa Having now described my invention what I claim is:

1. As new products, compounds of the general formula: 0

x H R wherein X and X represent hydrogen or a monovalent substituent,and R and R represent radicles of a compound obtainable by thecondensation of a chloronitroaryl compound, containing an acid residueof the group comprising SO H and COOH, with one amino group of anaromatic diamine, which compounds are soluble in water, soluble insulfuric acid with a characteristic coloration and, in a dry form, aredark-brown to black powders.

I i I]! N0 N0; N Ha N I k N NO N02 H H dyestufi after being isolatedfrom the lye forms, when dry, a black powder which dissolves in cone.sulfuric acid with a greyishgreen coloration and which dyes chromeleather a brown tint with a green hue.

The product has the probable formula:

(6 COONa 2. As new products, compounds of the general formula:

wherein X and X represent hydrogen or a monovalent substituent, and Rand R represent radicles of a compound obtainable by the condensation ofl-chlorol-nitrobenzene 2 sulfonic acid with one amino group of anaromatic diamine, which compounds are soluble in water, soluble insulfuric acid with a characteristic coloration and, in a dry form, aredark-brown to black powders.

3. As a new product, the dyestufi of the composition represented by theformula SOaNa H I 3 N 111 H f1 N02 g V g OH:

OaNa

being, in the dry form, a dark brown powder soluble in water with abrown color, soluble in concentrated sulfuric acid with a brown color,and dyeing wool and leather brown tints.

4. A process of making dyestuffs suitable for dyeing wool and leatherwhich comprises condensing a benzoquinone compound with a condensationproduct of the general formula:

I ay and n represents a whole number not more than 2, and in whicheither Y or R contains an acid residue of the group comprising SO H and-COOH.

In testimony whereof, I atfix my signature.

Rosana? SCHMIDLIN.

in which Y represents an aromatic residue

